Polymerization process and catalyst system

ABSTRACT

UTILIZATION OF A CATALYST SYSTEM FORMED BY ADMIXING (A) A COMPOUND OF THE FORMULA RNALX3-N, (B) A TITANIUM TRICHLORIDE-ALUMINUM TRICHLORIDE COMPLEX OF THE APPROXIMATE FORMULA TICL3.1/3ALCL3 AND (C) A COMPOUND OF THE FORMULA M(NR2)M IN THE POLYMERIZATION OF POLYMERS. IN THE RESULTS IN THE INCREASED PRODUCTION OF POLYMERS. IN THE ABOVE FORMULAS, R IS SELECTED FROM ALKYL, CYCLOALKYL AND ARYL GROUPS AND COMBINATONS THEREOF, HAVING FROM 1 TO 12 CARBON ATOMS, M IS A GROUP IV-A OR IV-B METAL, N IS 1, 2 OR MIXTURES THEREOF, X IS HALOGEN AND M IS THE VALENCE OF M.

United States Patent O 3,734,899 POLYMERIZATION PROCESS AND CATALYST SYSTEM Lawrence M. Fodor, Bartlesville, Okla., assignor to Phillips Petroleum Company No Drawing. Filed Nov. 20, 1969, Ser. No. 878,531

- Int. Cl. C08f 1/56, 3/10 US. Cl. 26093.7 6 Claims ABSTRACT OF THE DISCLOSURE Utilization of a catalyst system formed by admixing (a) a compound of the formula R- AlX (b) a titanium trichloride-aluminum trichloride complex of the approximate formula TiCl /3A1Cl and (c) a compound of the formula M(NR in the polymerization of l-olefin results in the increased production of polymers. In the above formulas, R is selected from alkyl, cycloalkyl and aryl groups and combinations thereof, having from 1 to 12 carbon atoms, M is a Group IV-A or IV-B metal, n is l, 2 or mixtures thereof, X is halogen and m is the valence of M.

BACKGROUND OF THE INVENTION Polymers of alpha-olefins, particularly of propylene, have long been known and numerous procedures have been disclosed for their production. However, not all such procedures are attractive due to their low productivity or their failure to produce a commercially useful product. It is, therefore, highly desirable to provide a system wherein there is achieved an increased production of useful polymer.

THE INVENTION It is thus an object of this invention to provide an improved process for the production of olefin polymers.

Another object of this invention is to provide a polymerization process in which there is obtained increased productivity.

A further object of this invention is to provide a novel catalyst system which, when employed in the polymerization of 1-olefin results in an increase in the productivity of the system.

' Other aspects, objects and the several advantages of this invention will be apparent to those skilled in the art upon consideration of this disclosure.

According to this invention, I have discovered that increased productivity of polymers of l-olefin (alphaolefins) can be obtained when the polymerization is conducted in the presence of a catalyst system formed by admixing (a) an organoaluminum compound or mixture of such compounds of the formula R,,AlX wherein R is alkyl, cycloalkyl, aryl or combinations thereof having 1 to 12 carbon atoms, X is a halogen and n is 1, 2 or mixtures thereof; (b) a titanium trichloride-aluminum trichloride complex such as that resulting from the reaction of titanium tetrachloride and aluminum and having the approximate formula TiCl /3A1Cl and (c) an adjuvant of the formula M(NR wherein M is a group IV-A or Group lV-B metal-germanium, tin, lead, titanium, zirconium, hafniumN is nitrogen, R is selected from alkyls, cycloalkyl and aryl radicals and combinations thereof having from 1 to 12 carbon atoms and m is the valence of M.

The enumeration of alkyl, cycloalkyl and aryl radicals herein in defining the formulas is intended to include the various mixed radicals such as alkaryl, aralkyl, alkylcycloalkyl, cycloalkylaryl, and the like.

The compounds and mixtures of compounds represented by the formula R,,AlX and utilized as comice ponent (a) of the catalyst system of the invention are well known in the art. Examples of such compounds are diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, and the like.

The titanium chloride-aluminum chloride complex utilized as component (b) of the catalyst system according to this invention is also well known in the art. It can be formed, for example, by reacting titanium tetrachloride with metallic aluminum. The complex can be represented by the formula TiCl /sAlCl Examples of the metal adjuvant compounds of the formula M(NR which are component (c) of the catalyst are Broad and preferred ranges for the molar ratio of the catalyst components are:

Ratio to TiCl %AlOla Broad Preferred RnAlXQ-n 0.5:1 to 10:1 1:1 to 7.521. M01112)... 0.01:1 to 3:1-. 0.5:1 to 2:1.

The total catalyst concentration is usually in the range of 0.005 to 10 weight percent of the olefin being polymerized, but concentrations outside this range are operative.

The polymerization reaction is carried out either in a mass system, i.e., the olefin being polymerized acts as the reaction medium, or in an inert hydrocarbon diluent, such as a paraflin, cycloparaffin, or aromatic hydrocarbon or mixtures thereof having up to 20 carbon atoms per molecule. Examples of hydrocarbons that can be used are pentane, hexane, isooctane, eicosane, cyclohexane, methylcyclopentane, benzene, toluene, naphthalene, anthracene, and the like. When an inert diluent is used, the volume ratio of diluent to olefin is in the range of 1:1 to 10:1, preferably 3:1 to 7:1.

The polymerization is conducted at temperatures in the range of to 250 F., preferably to 200 F. The pressure can be sufiicient to maintain the reaction mixture substantially in the liquid phase, or, particularly in a mass system, can be such that the olefin is in the vapor phase. The reaction time is in the range of 10 minutes to 75 hours, more frequently 30 minutes to 25 hours.

Although the invention is illustrated by the polymerization of propylene, any aliphatic l-olefin having up to 8 carbon atoms per molecule can be used. Preferably those having 3 to 7 carbon atoms are used, such as propylene, l-butene, l-hexene, 4-methyl-1-pentene, l-heptene, and the like. Copolymers of two or more of these olefins can be prepared using the catalyst composition of this invention.

4 chloride-aluminum trichloride complex of the flormula TiCl -/3AlCl and (c) tetrakis(dimethylamino) tin.

3. A process which comprises polymerizing an aliphatic l-olefin having from 3 to 8 carbon atoms per molecule in the presence of a catalyst which forms on mixing (a) a It is within the scope of the invention to use hydrogen compound of the formula R AlX wherein R 18 alkyl, in a concentration of about 0.08 to 1 mol percent of the cycloalkyl, aryl or combinations thereof having 1 to 12 propylene for controlling the molecular weight of the carbon atoms, X is a halogen, and n is 1, 1.5 or 2; (b) a polymer. titanium trichloride-aluminum trichloride complex of the The following example will further illustrate the informula TiCl-%AlCl and (c) an adjuvant of the vention, although it is not intended that the invention be formula M(NR wherein R is selected from alkyl, limited thereto. cycloalkyl and aryl radicals and combinations thereof hav- EXAMPLE ing from 1 to 12 carbon atoms, M is tin, and m is the Data illustrating the process of the invention were Y i i; of a ig i g ig obtained by polymerizing propylene in a 1-liter, stirred 1S m pg 0 f mo ar Ia 0 reactor in 2.5-hour runs at 130 F. and about 300 p.s.i.g. (c) to 15 mt e raflge o to 1 with 250 grams of propylene and 1.0 liter of hydrogen (at A process f f 3 w1 1erem 531d Patalyst 25 C. and 1 atmosphere) present in the reaction system. 15 formed by adn 11Xmg dlethflalunlmum Chlorldfi; A catalyst, there was employed a mixture f diethyl titanium trichloride-aluminum trichloride complex of the aluminum chloride, TiCl /3AlCl and adjuvant as noted formula TiC1s"/3A1C1a and tetrakiswlmethylamino) below. tin.

The following results were obtained: 5. A process according to claim 3 wherein the polym- Catalyst mol Wt. percent Flexural ratio DEAG: catalyst Xylenes e modulus Adjuvant: based on Producsolubles Melt p.s.i

Adjuvant Run N0. TiClgAA olefin tivlty (percent) flow X10- 1 (Control) 5.25101 0. 108 738 7. 1 8.73 183 SI1(N(CH3)2)4 2 3. 0:0. 05.1 0.129 826 3.7 3. 74 172 n(N(OHa)2)4---. 3--- 3.0:0.10=1 0.132 833 6.0 7.01 170 3)2)4-- 4- 3. mo. 20:1 0.139 816 4. 7 6. 29 184 a)2)4-- 5. 15: 1 :0 0. 0542 Trace s)2)4 6. 151120 0. 0542 Trace (N( a)2)4-. 7- 3=0.05;1 0.065 890 7 6 9.16 161 Ti(N(CHa)z)i 8 3:0.10:1 0.065 1,100 9.0 9. 39 176 Determined by placing 0.95 g. of polymer in a centrifuge tube, adding 95 ml. mixed xylenes, heatlng for 15 minutes at 285 F., cooling, centrifuging, evaporating the solvent from a -ml. aliquot of the supernatant hquld,

weighing the residue, and multiplying by 400.

ASTM 1) 1238-621, Condition L.

ASTM 1) 790-63.

'Ietrakis(dimethylamino) tin.

'Ietrakis(dimethylamino) titanium.

The above data demonstrate that utilization of the process and catalyst systems of this invention results in increased productivity of a useful olefin polymer.

Reasonable variations and modifications of this invention can be made, or followed, in view of the foregoing disclosure, without departing from the spirit or scope thereof.

I claim:

1. A catalyst system formed on admixing (a) a compound of the formula R AlX wherein R is an alkyl, cycloalkyl, aryl radical or combinations thereof having 1 to 12 carbon atoms, X is a halogen, and n is 1, 1.5 or 2; (b) a titanium trichloride-aluminum trichloride complex of the formula TiCl -%AlCl and (c) an adjuvant of the formula M(NR wherein R is selected from alkyl, cycloalkyl and aryl radicals and combinations thereof having from 1 to 12 carbon atoms, M is tin, and m is the valence of M, and wherein the molar ratio of (a) to (b) is in the range of 0.5 :1 to 10:1 and the molar ratio of (c) to (b) is in the range of 0.01:1 to 3:1.

2. A catalyst system according to claim 1 formed by admixing (a) diethylaluminum chloride; (b) titanium tri- UNITED STATES PATENTS 3,075,960 l/1963 Lovett et al 26093.7 3,173,901 3/1965 Newberg et al 260-94.9 3,182,049 5/1965 Moberly 260-93] 3,196,137 7/1965 Cain 26093.7 3,462,403 8/ 1969 Pendleton 260--93.7

JAMES A. SEIDLECK, Primary Examiner E. J. SMITH, Assistant Examiner U.S. Cl. X.R. 

